U.S. patent number 7,915,323 [Application Number 12/499,853] was granted by the patent office on 2011-03-29 for mono ethylenically unsaturated polycarbosiloxane monomers.
This patent grant is currently assigned to Bausch & Lamb Incorporated. Invention is credited to Alok Kumar Awasthi, Jay F. Kunzler, Jeffrey G. Linhardt, Jason K. Stanbro.
United States Patent |
7,915,323 |
Awasthi , et al. |
March 29, 2011 |
Mono ethylenically unsaturated polycarbosiloxane monomers
Abstract
The present invention relates to polymeric compositions useful
in the manufacture of biocompatible medical devices. More
particularly, the present invention relates to certain
monoethylenically unsaturated polycarbosiloxane monomers capable of
polymerization to form polymeric compositions having desirable
physical characteristics useful in the manufacture of ophthalmic
devices.
Inventors: |
Awasthi; Alok Kumar (Pittsford,
NY), Stanbro; Jason K. (Rochester, NY), Kunzler; Jay
F. (Canandaigua, NY), Linhardt; Jeffrey G. (Fairport,
NY) |
Assignee: |
Bausch & Lamb Incorporated
(Rochester, NY)
|
Family
ID: |
43427967 |
Appl.
No.: |
12/499,853 |
Filed: |
July 9, 2009 |
Prior Publication Data
|
|
|
|
Document
Identifier |
Publication Date |
|
US 20110009587 A1 |
Jan 13, 2011 |
|
Current U.S.
Class: |
523/106; 526/263;
526/320; 526/306; 526/264; 526/258; 526/319; 523/107; 528/37;
526/310; 526/303.1; 526/317.1 |
Current CPC
Class: |
G02B
1/043 (20130101); C08F 30/08 (20130101); G02B
1/043 (20130101); C08L 83/06 (20130101) |
Current International
Class: |
G02B
1/04 (20060101) |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Other References
Lai, Yu-Chin. "The Role of Bulky Polysiloxanylalkyl Methacrylates
in Oxygen-Permeable Hydrogel Materials" in J. Appl. Poly. Sci.,
vol. 56, pp. 317-324 (1995). cited by other .
Lai, Yu-Chin. "The Role of Bulky Polysiloxanylakyl Methacrylates in
Polyurethane-Polysiloxane Hydrogels" in J. App. Poly. Sci., vol.
60, pp. 1193-1199 (1996). cited by other .
Benjamin, William J. et al. "The Oxygen Permeability of Reference
Materials" in Optom. Vis. Sci., 74 (12s): 95 (1997). cited by other
.
Lohmeijer, Bas G.G. et al. "Organocatalytic Living Ring-Opening
Polymerization of Cyclic Carbosiloxanes" in Organic Letters, vol.
8, No. 21, pp. 4683-4686 (2006). cited by other .
Lu, Ping et al."Reaction of Dimethyldichlorosilane,
Phenylmethyldichlorosilane, or Diphenyldichlorosilane with Dimethyl
Sulfoxide" in Organometallics, 1996, 15, pp. 4649-4652. cited by
other .
Piccoli, William et al. "Highly Strained Cyclic-Paraffin Siloxanes"
in Organic and Biological Chemistry, Apr. 20, 1960, vol. 82, pp.
1883-1885. cited by other .
Ziatdinov, Vadim et al. Anionic Ring-Opening Polymerization of
Trimethylsiloxy-Substituted 1-Oxa-2,5-disilacyclopentanes . . . :
in Macromolecules, 2002, vol. 35, pp. 2892-2897. cited by other
.
U.S. Appl. No. 12/499,854, filed Jul. 9, 2009, Awasthi et al. cited
by other.
|
Primary Examiner: Zimmer; Marc S
Attorney, Agent or Firm: Smith; Glenn D.
Claims
What is claimed is:
1. A monomer mix useful for forming a medical device wherein the
monomer mix comprises at least one monomer selected from the group
consisting of the monomers having the following formula (I):
##STR00027## wherein X is the residue of a ring opening agent, L is
the same or different and is a linker group or a bond and V is an
ethylenically unsaturated polymerizable group, R.sub.1, R.sub.2,
R.sub.3, R.sub.4, R.sub.5, R.sub.6 are independently H, alkyl, halo
alkyl, cyclo alkyl, heterocyclo alkyl, alkenyl, halo alkenyl, or
aromatic, R.sub.7 and R.sub.8 are independently H or alkyl wherein
at least one of R.sub.7 or R.sub.8 is hydrogen, y is 2-7 and n is
1-100 and when polymerized forms a medical device.
2. A monomer mix useful for forming a medical device wherein the
monomer mix comprises at least one monomer selected from the group
consisting of the monomers having the following formula (II)
##STR00028## wherein L is the same or different and is a linker
group or a bond and V is the same or different and is an
ethylenically unsaturated polymerizable group, R.sub.1, R.sub.2,
R.sub.3, R.sub.4, R.sub.5, R.sub.6 and R.sub.9 are independently H,
alkyl, halo alkyl, cyclo alkyl, heterocyclo alkyl, alkenyl, halo
alkenyl, or aromatic, R.sub.7 and R.sub.8 are independently H or
alkyl wherein at least one of R.sub.7 or R.sub.8 is hydrogen, y is
2-7 and n is 1-100 and when polymerized forms a medical device.
3. The monomer mix of claim 1 further comprising a second
copolymerizable second monomer.
4. The monomer mix of claim 2 further comprising a second
copolymerizable second monomer.
5. The monomer mix of claim 1 wherein the medical device formed is
selected from the group consisting of rigid contact lenses, soft
contact lenses, phakic intraocular lenses, aphakic intraocular
lenses and corneal implants.
6. The monomer mix of claim 2 wherein the medical device formed is
selected from the group consisting of rigid contact lenses, soft
contact lenses, phakic intraocular lenses, aphakic intraocular
lenses and corneal implants.
7. The monomer mix of claim 1 wherein the medical device formed is
selected from the group consisting of artificial heart valves,
films, surgical devices, vessel substitutes, intrauterine devices,
membranes, diaphragms, surgical implants, artificial blood vessels,
artificial ureters, artificial breast tissue, membranes intended to
come into contact with body fluid outside of the body, membranes
for kidney dialysis machines, membranes for heart/lung machines,
catheters, mouth guards, denture liners, ophthalmic devices, and
hydrogel contact lenses.
8. The monomer mix of claim 2 wherein the medical device formed is
selected from the group consisting of artificial heart valves,
films, surgical devices, vessel substitutes, intrauterine devices,
membranes, diaphragms, surgical implants, artificial blood vessels,
artificial ureters, artificial breast tissue, membranes intended to
come into contact with body fluid outside of the body, membranes
for kidney dialysis machines, membranes for heart/lung machines,
catheters, mouth guards, denture liners, ophthalmic devices, and
hydrogel contact lenses.
9. The monomer mix of claim 7 wherein the medical device is a
hydrogel contact lens.
10. The monomer mix of claim 8 wherein the medical device is a
hydrogel contact lens.
11. The monomer mix of claim 1 wherein the mono ethylenically
unsaturated carbosiloxane monomer is present in an amount from
about 0.1 to about 30 percent by weight of the monomer mix.
12. The monomer mix of claim 1 wherein the mono ethylenically
unsaturated carbosiloxane monomer is present in an amount from
about 0.1 to about 20 percent by weight of the monomer mix.
13. The monomer mix of claim 1 wherein the mono ethylenically
unsaturated carbosiloxane monomer is present in an amount from
about 5 to about 15 percent by weight of the monomer mix.
14. The monomer mix of claim 2 wherein the mono ethylenically
unsaturated carbosiloxane monomer is present in an amount from
about 0.1 to about 30 percent by weight of the monomer mix.
15. The monomer mix of claim 2 wherein the mono ethylenically
unsaturated carbosiloxane monomer is present in an amount from
about 0.1 to about 20 percent by weight of the monomer mix.
16. The monomer mix of claim 2 wherein the mono ethylenically
unsaturated carbosiloxane monomer is present in an amount from
about 5 to about 15 percent by weight of the monomer mix.
17. The monomer mix of claim 3 wherein the second copolymerizable
second monomer is a hydrophobic silicone containing monomer.
18. The monomer mix of claim 17 wherein the hydrophobic silicone
containing monomer is present in the monomer mix between about 0.1
to about 75.8 percent by weight.
19. The monomer mix of claim 17 wherein the hydrophobic silicone
containing monomer is present in the monomer mix between about 2 to
about 20 percent by weight.
20. The monomer mix of claim 17 wherein the hydrophobic silicone
containing monomer is present in the monomer mix between about 5 to
about 13 percent by weight.
21. The monomer mix of claim 4 wherein the second copolymerizable
second monomer is a hydrophobic silicone containing monomer.
22. The monomer mix of claim 21 wherein the hydrophobic silicone
containing monomer is present in the monomer mix between about 0.1
to about 75.8 percent by weight.
23. The monomer mix of claim 21 wherein the hydrophobic silicone
containing monomer is present in the monomer mix between about 2 to
about 20 percent by weight.
24. The monomer mix of claim 21 wherein the hydrophobic silicone
containing monomer is present in the monomer mix between about 5 to
about 13 percent by weight.
25. The monomer mix of claim 3 wherein the second copolymerizable
monomer is a non-silicone containing hydrophobic monomer.
26. The monomer mix of claim 4 wherein the second copolymerizable
monomer is a non-silicone containing hydrophobic monomer.
27. The monomer mix of claim 3 wherein the non-silicone containing
hydrophobic monomer is present at about 0 to about 60 percent by
weight.
28. The monomer mix of claim 4 wherein the non-silicone containing
hydrophobic monomer is present at about 0 to about 60 percent by
weight.
29. The monomer mix of claim 3 wherein the non-silicone containing
hydrophobic monomer is selected from the group consisting of alkyl
acrylates and alkyl methacrylates.
30. The monomer mix of claim 4 wherein the non-silicone containing
hydrophobic monomer is selected from the group consisting of alkyl
acrylates and alkyl methacrylates.
31. The monomer mix of claim 3 wherein the second copolymerizable
monomer is a bulky monomers selected from the group consisting of
methacryloxypropyl tris(trimethylsiloxy)silane ("TRIS"),
pentamethyldisiloxanyl methylmethacrylate,
tris(trimethylsiloxy)methacryloxy propylsilane,
phenyltretramethyl-disloxanylethyl acrylate,
methyldi(trimethylsiloxy)methacryloxymethyl silane,
3-[tris(trimethylsiloxy)silyl]propyl vinyl carbamate,
3[tris(trimethylsiloxy)silyl]propyol ally carbamate, and
3-[tris(trimethylsiloxy)silyl]propyl vinyl carbonate.
32. The monomer mix of claim 4 wherein the second copolymerizable
monomer is a bulky monomers selected from the group consisting of
methacryloxypropyl tris(trimethylsiloxy)silane ("TRIS"),
pentamethyldisiloxanyl methylmethacrylate,
tris(trimethylsiloxy)methacryloxy propylsilane,
phenyltretramethyl-disloxanylethyl acrylate,
methyldi(trimethylsiloxy)methacryloxymethyl silane,
3-[tris(trimethylsiloxy)silyl]propyl vinyl carbamate,
3[tris(trimethylsiloxy)silyl]propyol allyl carbamate, and
3-[tris(trimethylsiloxy)silyl]propyl vinyl carbonate.
33. The monomer mix of claim 31 wherein the bulky monomer is
present at about 0 to about 41.2 percent by weight.
34. The monomer mix of claim 31 wherein the bulky monomer is
present at about 34 to about 41 percent by weight.
35. The monomer mix of claim 31 wherein the bulky monomer is
present at about 0 to about 25 to about 41 percent by weight.
36. The monomer mix of claim 32 wherein the bulky monomer is
present at about 0 to about 41.2 percent by weight.
37. The monomer mix of claim 32 wherein the bulky monomer is
present at about 34 to about 41 percent by weight.
38. The monomer mix of claim 32 wherein the bulky monomer is
present at about 0 to about 25 to about 41 percent by weight.
39. The monomer mix of claim 9 wherein the monomer mix comprises a
mixture containing at least one silicone-containing monomer and at
least one hydrophilic monomer.
40. The monomer mix of claim 9 wherein the monomer mix comprises a
separate crosslinker.
41. The monomer mix of claim 40 wherein the separate crosslinker is
selected from the group consisting of methacrylates, ethylene
glycol dimethacrylate (EGDMA) and ally methacrylate (AMA).
42. The monomer mix of claim 41 wherein the separate crosslinker is
present at between about 0 to about 76 percent by weight.
43. The monomer mix of claim 41 wherein the separate crosslinker is
present at between about 2 to about 20 percent by weight.
44. The monomer mix of claim 41 wherein the separate crosslinker is
present at between about 5 to about 13 percent by weight.
45. The monomer mix of claim 10 wherein the silicone-containing
monomer is a crosslinking agent.
46. The monomer mix of claim 3 wherein the second copolymerizable
monomer is a hydrophilic monomer.
47. The monomer mix of claim 46 wherein the hydrophilic monomer is
selected from the group consisting of unsaturated carboxylic acids,
methacrylic acids, acrylic acids; acrylic substituted alcohols,
2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate; vinyl
lactams, N-vinylpyrrolidone (NVP), 1-vinylazonan-2-one;
acrylamides, methacrylamide, N,N-dimethylacrylamide (DMA) and
mixtures thereof.
48. The monomer mix of claim 46 wherein the hydrophilic monomer is
present, separately or by combined weight in amounts of between
about 0 to about 60 percent by weight.
49. The monomer mix of claim 46 wherein the hydrophilic monomer is
present, separately or by combined weight in amounts between about
20 to about 45 percent by weight.
50. The monomer mix of claim 46 wherein the hydrophilic monomer is
present, separately or by combined weight in amounts between about
0 to about 48.6 percent by weight.
51. The monomer mix of claim 46 wherein the hydrophilic monomer is
present, separately or by combined weight in amounts between about
0 to about 30 percent by weight.
52. The monomer mix of claim 46 wherein the hydrophilic monomer is
present, separately or by combined weight in amounts between about
0 to about 25 percent by weight.
53. The monomer mix of claim 46 wherein the hydrophilic monomer is
present, separately or by combined weight in amounts between about
0 to about 9.5 percent by weight.
54. The monomer mix of claim 46 wherein the hydrophilic monomer is
present, separately or by combined weight in amounts between about
2 to about 7 percent by weight.
55. The monomer mix of claim 4 wherein the second copolymerizable
monomer is a hydrophilic monomer.
56. The monomer mix of claim 55 wherein the hydrophilic monomer is
selected from the group consisting of unsaturated carboxylic acids,
methacrylic acids, acrylic acids; acrylic substituted alcohols,
2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate; vinyl
lactams, N-vinylpyrrolidone (NVP), 1-vinylazonan-2-one;
acrylamides, methacrylamide, N,N-dimethylacrylamide (DMA) and
mixtures thereof.
57. The monomer mix of claim 55 wherein the hydrophilic monomer is
present, separately or by combined weight in amounts of between
about 0 to about 60 percent by weight.
58. The monomer mix of claim 55 wherein the hydrophilic monomer is
present, separately or by combined weight in amounts between about
20 to about 45 percent by weight.
59. The monomer mix of claim 55 wherein the hydrophilic monomer is
present, separately or by combined weight in amounts between about
0 to about 48.6 percent by weight.
60. The monomer mix of claim 55 wherein the hydrophilic monomer is
present, separately or by combined weight in amounts between about
0 to about 30 percent by weight.
61. The monomer mix of claim 55 wherein the hydrophilic monomer is
present, separately or by combined weight in amounts between about
0 to about 25 percent by weight.
62. The monomer mix of claim 55 wherein the hydrophilic monomer is
present, separately or by combined weight in amounts between about
0 to about 9.5 percent by weight.
63. The monomer mix of claim 55 wherein the hydrophilic monomer is
present, separately or by combined weight in amounts between about
2 to about 7 percent by weight.
64. The monomer mix of claim 17 further comprising an organic
diluent.
65. The monomer mix of claim 64 wherein the organic diluent is
selected from the group consisting of alcohols, tent-butanol (TBA),
tert-amyl alcohol, hexanol and nonanol; diols, ethylene glycol;
polyols, glycerol and mixtures thereof.
66. The monomer mix of claim 64 wherein the organic diluent is
present at about 0 to about 60% by weight of the monomeric
mixture.
67. The monomer mix of claim 64 wherein the organic diluent is
present at about 1 to about 40% by weight.
68. The monomer mix of claim 64 wherein the organic diluent is
present at about 2 to about 30% by weight.
69. The monomer mix of claim 64 wherein the organic diluent is
present at about 3 to about 25% by weight.
70. The monomer mix of claim 21 further comprising an organic
diluent.
71. The monomer mix of claim 70 wherein the organic diluent is
selected from the group consisting of alcohols, tert-butanol (TBA),
tert-amyl alcohol, hexanol and nonanol; diols, ethylene glycol;
polyols, glycerol and mixtures thereof.
72. The monomer mix of claim 70 wherein the organic diluent is
present at about 0 to about 60% by weight of the monomeric
mixture.
73. The monomer mix of claim 70 wherein the organic diluent is
present at about 1 to about 40% by weight.
74. The monomer mix of claim 70 wherein the organic diluent is
present at about 2 to about 30% by weight.
75. The monomer mix of claim 70 wherein the organic diluent is
present at about 3 to about 25% by weight.
76. A hydrogel contact lens comprising a polymerized monomer mix
comprising a polymerizable monomer mixture comprising about 0.1 to
about 75.8 percent by weight of a methacrylamide crosslinker, about
0 to about 41.2 percent by weight of a bulky siloxane monomer,
about 0 to about 78 percent by weight of at least one hydrophilic
monomer, about 0 to about 48.6 percent by weight of an alcohol,
about 0.1 to about 29.9 weight percent of an mono ethylenically
unsaturated carbosiloxane monomer, about 0.1 to about 1.0 percent
by weight of an initiator and about 90 to about 200 parts per
million of a visibility tint.
77. The hydrogel contact lens of claim 76 comprising as part of
polymerizable monomer mixture comprising about 5 to about 13
percent by weight of a methacrylamide crosslinker, about 34 to
about 41 percent by weight of a bulky siloxane monomer, about 28 to
about 52 percent by weight of at least one hydrophilic monomer,
about 0 to about 25 percent by weight of an alcohol, about 5 to
about 15 weight percent of an mono ethylenically unsaturated
carbosiloxane monomer, about 0.2 to about 0.8 percent by weight of
an initiator and about 90 to about 145 parts per million of a
visibility tint.
78. The hydrogel contact lens of claim 76 comprising as part of
polymerizable monomer mixture comprising about 2 to about 8 percent
by weight of a methacrylamide crosslinker, about 25 to about 38
percent by weight of a bulky siloxane monomer, about 35 to about 45
percent by weight of at least one hydrophilic monomer, about 3 to
about 8 percent by weight of an alcohol, about 10 to about 13
weight percent of an mono ethylenically unsaturated carbosiloxane
monomer, about 0.3 to about 0.6 percent by weight of an initiator
and about 145 to about 200 parts per million of a visibility tint.
Description
PRIORITY CLAIMS TO PRIOR APPLICATIONS
None
CROSS-REFERENCE TO RELATED APPLICATIONS
None
FIELD
The present invention relates to novel monomers useful in the
manufacture of biocompatible medical devices. More particularly,
the present invention relates to certain monomer mixes containing
monomers based on mono ethylenically unsaturated polycarbosiloxane
monomers capable of polymerization to form polymeric compositions
having desirable physical characteristics useful in the manufacture
of ophthalmic devices. Such properties include low modulus of
elasticity and improved hydrolytic stability. The present invention
also relates to medical devices formed from the monomer mixes
containing monomers based on mono ethylenically unsaturated
polycarbosiloxane monomers.
BACKGROUND AND SUMMARY
Various articles, including biomedical devices, are formed of
organosilicon-containing materials. One class of
organosilicon-containing materials useful for biomedical devices,
such as soft contact lenses, is silicone-containing hydrogel
materials. A hydrogel is a hydrated, crosslinked polymeric system
that contains water in an equilibrium state. Hydrogel contact
lenses offer relatively high oxygen permeability as well as
desirable biocompatibility and comfort. The inclusion of a
silicone-containing material in the hydrogel formulation generally
provides higher oxygen permeability since silicone based materials
have higher oxygen permeability than water.
Organosilicon-containing materials useful for biomedical devices,
including contact lenses, are disclosed in the following U.S. Pat.
No. 4,208,506 (Deichert et al.); U.S. Pat. No. 4,686,267 (Ellis et
al.); U.S. Pat. No. 5,034,461 (Lai et al.); and U.S. Pat. No.
5,070,215 (Bambury et al.).
U.S. Pat. Nos. 5,358,995 and 5,387,632 describe hydrogels made from
various combinations of silicone macromers, TRIS, n-vinyl
pyrrolidone (NVP) and DMA. Replacing a substantial portion of the
silicone macromer with TRIS reduced the modulus of the resulting
hydrogels. Two publications from the same author, "The Role of
Bulky Polysiloxanylalkyl Methacrylates in Polyurethane-Polysiloxane
Hydrogels", J. Appl. Poly. Sci., Vol. 60, 1193-1199 (1996), and
"The Role of Bulky Polysiloxanylalkyl Methacrylates in
Oxygen-Permeable Hydrogel Materials", J. Appl. Poly. Sci., Vol. 56,
317-324 (1995) also describe experimental results indicating that
the modulus of hydrogels made from reaction mixtures of
silicone-macromers and hydrophilic monomers such as DMA decreases
with added TRIS. The addition of
methacryloxypropyltris(trimethylsiloxy)silane (TRIS) reduced the
modulus of such hydrogels, but in many examples the modulus was
still higher than may be desired.
U.S. Pat. No. 4,208,506 describes monomeric polyparaffinsiloxanes
end-capped with activated unsaturated groups and polymers and
copolymers thereof. The monomers of U.S. Pat. No. 4,208,506 are
cross-linkers. We have discovered that mono ethylenically
unsaturated polycarbosiloxane monomers are advantageous in device
forming monomer mixes because in addition to reducing the crosslink
density of the polymerized mixture the additional chain length of
the alkyl portion of the monomer backbone reduces the modulus of
the polymerized monomer mix.
There still remains a need in the art for silicone hydrogels which
are soft enough to make soft contact lenses, which possess high
oxygen permeability, suitable water content, and sufficient
elasticity, and are comfortable to the contact lens wearer.
BRIEF DESCRIPTION OF THE DRAWINGS
None.
DETAILED DESCRIPTION
Unless clearly stated otherwise all materials used in forming a
monomer mix are listed as weight percent. Also, unless clearly
stated otherwise it will be understood that all amounts of
materials used to make the monomers and monomer mixes disclosed
herein represent the statistical mean of a normal distribution of
weight values such as are ordinarily encountered in the laboratory
or commercial manufacture of the monomers and monomer mixes
disclosed herein. Therefore, unless clearly stated otherwise, all
numerical values shall be understood as being modified by the term
"about".
In a first aspect, the invention relates to monomers of formula
(I):
##STR00001## wherein X is the residue of a ring opening agent; L is
the same or different and is a linker group or a bond; V is an
ethylenically unsaturated polymerizable group; R.sub.1, R.sub.2,
R.sub.3, R.sub.4, R.sub.5, R.sub.6 are independently H, alkyl, halo
alkyl, cyclo alkyl, heterocyclo alkyl, alkenyl, halo alkenyl, or
aromatic; R.sub.7 and R.sub.8 are independently H or alkyl wherein
at least one of R.sub.7 or R.sub.8 is hydrogen; y is 2-7 and n is
1-100.
Ring opening agents are well known in the literature. Non-limiting
examples of anionic ring opening agents include alkyl lithiums,
alkoxides, trialkylsiloxylithium wherein the alkyl group may or may
not contain halo atoms.
Linker groups can be any divalent radical or moiety and include
substituted or unsubstituted alkyl, alkyl ether, alkenyls, alkenyl
ethers, halo alkyls, substituted or unsubstituted siloxanes, and
monomers capable of propagating ring opening.
Ethylenically unsaturated polymerizable groups are well known to
those skilled in the art. Non-limiting examples of ethylenically
unsaturated polymerizable groups would include acrylates,
methacrylates, vinyl carbonates, O-vinyl carbamates, N-vinyl
carbamates, acrylamides and methacrylamides.
Additional preferred embodiments of the monomers of the invention
herein would include monomers of formula (II):
##STR00002## wherein L is the same or different and is a linker
group or a bond; V is the same or different and is an ethylenically
unsaturated polymerizable group; R.sub.1, R.sub.2, R.sub.3,
R.sub.4, R.sub.5, R.sub.6 and R.sub.9 are independently H, alkyl,
halo alkyl, cyclo alkyl, heterocyclo alkyl, alkenyl, halo alkenyl,
or aromatic; R.sub.7 and R.sub.8 are independently H or alkyl
wherein at least one of R.sub.7 or R.sub.8 is hydrogen; y is 2-7
and n is 1-100.
Additional preferred embodiments of the monomers of the invention
herein would include monomers of the following formulas III and
IV:
##STR00003## wherein R.sub.9, R.sub.10 and R.sub.11 are
independently H, alkyl, haloalkyl or other substituted alkyl
groups; n is as defined above and n.sup.1 is 0-10; and,
##STR00004## wherein n is 1-100, preferably n is 2-80, more
preferably n is 3-20, most preferably n is 5-15.
Additional preferred embodiments of the monomers of the invention
herein would include monomers of the following formulas V-IX:
##STR00005##
Additional preferred embodiments of the monomers of the invention
herein would include monomers of the following formulas X-XII:
##STR00006## wherein R.sub.9, R.sub.10 and R.sub.11 are
independently H, alkyl, haloalkyl or other substituted alkyl groups
and n and n.sup.1 are as defined above.
Additional preferred embodiments of the monomers of the invention
herein would include monomers of the following formulas
XIII-XV:
##STR00007## wherein n is as defined above and X.sup.- is a
counterion to provide an overall neutral charge.
Counterions capable of providing an overall neutral charge are well
known to those of ordinary skill in the art and would include, for
example, halide ions.
An additional preferred embodiment of the monomers of the invention
herein would include the monomer of the following formula XVI:
(M1-EDS7-D.sub.37-TMS)
##STR00008##
Monomers of formula I can be prepared by various synthetic methods,
for example:
##STR00009## ##STR00010##
Monomers of formula II can be prepared by various synthetic
methods, for example as shown in Example 6.
The term "monomer" used herein refers to varying molecular weight
compounds (i.e. typically having number average molecular weights
from about 700 to about 100,000) that can be polymerized, and to
medium to high molecular weight compounds or polymers, sometimes
referred to as macromonomers, (i.e., typically having number
average molecular weights greater than 700) containing functional
groups capable of further polymerization. Thus, it is understood
that the terms "organosilicon-containing monomers",
"silicone-containing monomers" and "hydrophilic monomers" include
monomers, macromonomers and prepolymers. Prepolymers are partially
polymerized monomers or monomers which are capable of further
polymerization.
An "organosilicon-containing monomer" contains at least one
[--Si--O-] or at least one [--Si--(C.sub.2-C.sub.7 alkyl) --Si--O-]
repeating units, in a monomer, macromer or prepolymer. Preferably,
the total Si and attached O are present in the
organosilicon-containing monomer in an amount greater than 5 weight
percent, and more preferable greater than 30 weight percent of the
total molecular weight of the organosilicon-containing monomer. A
"silicone-containing monomer" is one that contains at least one
[--Si--O-] repeating units, in a monomer, macromer or
prepolymer.
In yet another aspect, the invention includes articles formed of
device forming monomer mixes comprising, alone or in combination,
any of the monomers of formulas I-XVI. According to preferred
embodiments, the article is the polymerization product of a mixture
comprising at least one of the aforementioned monomers of formulas
I-XVI and at least a second copolymerizable monomer. The invention
is applicable to a wide variety of polymeric materials, either
rigid or soft. Especially preferred polymeric materials are lenses
including contact lenses, phakic and aphakic intraocular lenses and
corneal implants although all polymeric materials including
biomaterials are contemplated as being within the scope of this
invention. Preferred articles are optically clear and useful as a
contact lens.
The monomer mix of the present invention also provides medical
devices such as artificial heart valves, films, surgical devices,
vessel substitutes, intrauterine devices, membranes, diaphragms,
surgical implants, artificial blood vessels, artificial ureters,
artificial breast tissue and membranes intended to come into
contact with body fluid outside of the body, e.g., membranes for
kidney dialysis and heart/lung machines and the like, catheters,
mouth guards, denture liners, ophthalmic devices, and especially
hydrogel contact lenses.
Unless clearly stated otherwise it will be understood that all
amounts of materials used to make the monomers and monomer mixes
disclosed herein represent the statistical mean of a normal
distribution of weight values such as are ordinarily encountered in
the laboratory or commercial manufacture of the monomers and
monomer mixes disclosed herein. Therefore, unless clearly stated
otherwise, all numerical values shall be understood as being
modified by the term "about".
Useful concentration of the mono ethylenically unsaturated
polycarbosiloxane monomers of the invention herein would be 0.1 to
30 percent by weight of the monomer mix. More preferred
concentrations are 0.1 to 20 percent by weight. Even more preferred
concentrations would be 5 to 15 percent by weight.
Preferred compositions have both hydrophilic and hydrophobic
monomers. Depending upon the specific application, useful articles
made with these materials may require additional (other than the
subject mono ethylenically unsaturated polycarbosiloxane monomers)
hydrophobic, possibly silicone containing monomers. These
additional silicone containing hydrophobic monomers will be present
at between 0.1 to 75.8 percent by weight, more preferably between 2
to 20 percent by weight, even more preferably between 5 to 13
percent by weight. Amounts of non-silicone containing hydrophobic
monomers will be 0 to 60 percent by weight. Examples of
non-silicone hydrophobic materials include alkyl acrylates and
methacrylates. Especially preferred is silicone-containing
hydrogels.
Depending upon the application, useful articles may also require
bulky monomers such as those disclosed in U.S. Pat. No. 6,921,802
which include methacryloxypropyl tris(trimethylsiloxy)silane
("TRIS"), pentamethyldisiloxanyl methylmethacrylate,
tris(trimethylsiloxy)methacryloxy propylsilane,
phenyltretramethyl-disloxanylethyl acrylate,
methyldi(trimethylsiloxy)methacryloxymethyl silane,
3-[tris(trimethylsiloxy)silyl]propyl vinyl carbamate,
3[tris(trimethylsiloxy)silyl]propyol allyl carbamate, and
3-[tris(trimethylsiloxy)silyl]propyl vinyl carbonate. These bulky
monomers, when present, may be present at 0 to 41.2 percent by
weight, 34 to 41 percent by weight or even 25 to 41 percent by
weight.
Silicone-containing hydrogels are prepared by polymerizing a
mixture containing at least one silicone-containing monomer and at
least one hydrophilic monomer. The silicone-containing monomer may
function as a crosslinking agent (a crosslinker being defined as a
monomer having multiple polymerizable functionalities) or a
separate crosslinker may be employed. Hydrophobic crosslinkers
would include methacrylates such as ethylene glycol dimethacrylate
(EGDMA) and allyl methacrylate (AMA). Amounts of cross-linker would
be between 0 to 76 percent by weight, 2 to 20 percent by weight or
5 to 13 percent by weight.
The mono ethylenically unsaturated polycarbosiloxane monomers of
the invention herein may be copolymerized with a wide variety of
hydrophilic monomers to produce silicone hydrogel lenses. Suitable
hydrophilic monomers include: unsaturated carboxylic acids, such as
methacrylic and acrylic acids; acrylic substituted alcohols, such
as 2-hydroxyethyl methacrylate and 2-hydroxyethyl acrylate; vinyl
lactams, such as N-vinylpyrrolidone (NVP) and 1-vinylazonan-2-one;
and acrylamides, such as methacrylamide and N,N-dimethylacrylamide
(DMA). These hydrophilic monomers will be present, separately or by
combined weight in amounts of between 0 to 60 percent by weight,
between 20 to 45 percent by weight, between 0 to 48.6 percent by
weight, between 0 to 30 percent by weight, between 0 to 25 percent
by weight, between 0 to 9.5 percent by weight or between 2 to 7
percent by weight.
Other examples of silicone-containing monomer mixtures which may be
used with this invention include the following: vinyl carbonate and
vinyl carbamate monomer mixtures as disclosed in U.S. Pat. Nos.
5,070,215 and 5,610,252 (Bambury et al); fluorosilicon monomer
mixtures as disclosed in U.S. Pat. Nos. 5,321,108; 5,387,662 and
5,539,016 (Kunzler et al.); fumarate monomer mixtures as disclosed
in U.S. Pat. Nos. 5,374,662; 5,420,324 and 5,496,871 (Lai et al.)
and urethane monomer mixtures as disclosed in U.S. Pat. Nos.
5,451,651; 5,648,515; 5,639,908 and 5,594,085 (Lai et al.), all of
which are commonly assigned to assignee herein Bausch & Lomb
Incorporated, and the entire disclosures of which are incorporated
herein by reference. Other suitable hydrophilic monomers will be
apparent to one skilled in the art.
An organic diluent may be included in the initial monomeric
mixture. As used herein, the term "organic diluent" encompasses
organic compounds which minimize incompatibility of the components
in the initial monomeric mixture and are substantially nonreactive
with the components in the initial mixture. Additionally, the
organic diluent serves to minimize phase separation of polymerized
products produced by polymerization of the monomeric mixture. Also,
the organic diluent will generally be relatively
non-inflammable.
Contemplated organic diluents include alcohols such as tert-butanol
(TBA), tert-amyl alcohol, hexanol and nonanol; diols, such as
ethylene glycol; and polyols, such as glycerol. Preferably, the
organic diluent is sufficiently soluble in the extraction solvent
to facilitate its removal from a cured article during the
extraction step. Other suitable organic diluents would be apparent
to a person of ordinary skill in the art.
The organic diluent is included in an amount effective to provide
the desired effect (for example, minimal phase separation of
polymerized products). Generally, the diluent is included at 0 to
60% by weight of the monomeric mixture, with 1 to 40% by weight
being more preferred, 2 to 30% by weight being even more preferred
and 3 to 25% by weight being especially preferred.
According to the present process, the monomeric mixture, comprising
at least one hydrophilic monomer, at least one mono ethylenically
unsaturated polycarbosiloxane monomer and optionally the organic
diluent, is shaped and cured by conventional methods such as static
casting or spincasting.
Lens formation can be by free radical polymerization such as
azobisisobutyronitrile (AIBN) and peroxide catalysts using
initiators and under conditions such as those set forth in U.S.
Pat. No. 3,808,179, incorporated herein by reference.
Photoinitiation of polymerization of the monomer mixture as is well
known in the art may also be used in the process of forming an
article as disclosed herein. Colorants and the like may be added
prior to monomer polymerization.
Subsequently, a sufficient amount of unreacted monomer and, when
present, organic diluent is removed from the cured article to
improve the biocompatibility of the article. Release of
non-polymerized monomers into the eye upon installation of a lens
can cause irritation and other problems. Therefore, once the
biomaterials formed from the polymerized monomer mix containing the
monomers disclosed herein are formed they are then extracted to
prepare them for packaging and eventual use. Extraction is
accomplished by exposing the polymerized materials to various
solvents such as water, 2-propanol, etc. for varying periods of
time. For example, one extraction process is to immerse the
polymerized materials in water for about three minutes, remove the
water and then immerse the polymerized materials in another aliquot
of water for about three minutes, remove that aliquot of water and
then autoclave the polymerized material in water or buffer
solution.
Following extraction of unreacted monomers and any organic diluent,
the shaped article, for example an RGP lens, is optionally machined
by various processes known in the art. The machining step includes
lathe cutting a lens surface, lathe cutting a lens edge, buffing a
lens edge or polishing a lens edge or surface. The present process
is particularly advantageous for processes wherein a lens surface
is lathe cut, since machining of a lens surface is especially
difficult when the surface is tacky or rubbery.
Generally, such machining processes are performed before the
article is released from a mold part. After the machining
operation, the lens can be released from the mold part and
hydrated. Alternately, the article can be machined after removal
from the mold part and then hydrated.
The following examples are provided to enable one skilled in the
art to practice the invention and are merely illustrative of the
invention. The examples should not be read as limiting the scope of
the invention as defined in the claims.
EXAMPLES
All solvents and reagents were obtained from commercially available
sources and used as received.
Analytical Measurements
ESI-TOF MS: The electrospray (ESI) time of flight (TOF) MS analysis
was performed on an Applied Biosystems Mariner instrument. The
instrument operated in positive ion mode. The instrument was mass
calibrated with a standard solution containing lysine,
angiotensinogen, bradykinin (fragment 1-5) and des-Pro bradykinin.
This mixture provides a seven-point calibration from 147 to 921
m/z. The applied voltage parameters were optimized from signal
obtained from the same standard solution. For exact mass
measurements poly(ethylene glycol) (PEG), having a nominal M.sub.n
value of 400 Da, was added to the sample of interest and used as an
internal mass standard. Two PEG oligomers that bracketed the sample
mass of interest were used to calibrate the mass scale. Samples
were prepared as 30 .mu.M solutions in isopropanol (IPA) with the
addition of 2% by volume saturated NaCl in IPA. Samples were
directly infused into the ESI-TOF MS instrument at a rate of 35
.mu.L/min. A sufficient resolving power (6000 RP m/.DELTA.m FWHM)
was achieved in the analysis to obtain the monoisotopic mass for
each sample. In each analysis the experimental monoisotopic mass
was compared to the theoretical monoisotopic mass as determined
from the respective elemental compositions. In each analysis the
monoisotopic mass comparison was less than 10 ppm error. It should
be noted that uncharged samples have a sodium (Na) atom included in
their elemental composition. This Na atom occurs as a necessary
charge agent added in the sample preparation procedure. Some
samples do not require an added charge agent since they contain a
charge from the quaternary nitrogen inherent to their respective
structure.
GC: Gas chromatography was performed using a Hewlett Packard HP
6890 Series GC System. Purities were determined by integration of
the primary peak and comparison to the normalized
chromatograph.
NMR: .sup.1H-NMR characterization was carried out using a 400 MHz
Varian spectrometer using standard techniques in the art. Samples
were dissolved in chloroform-d (99.8 atom % D), unless otherwise
noted. Chemical shifts were determined by assigning the residual
chloroform peak at 7.25 ppm. Peak areas and proton ratios were
determined by integration of baseline separated peaks. Splitting
patterns (s=singlet, d=doublet, t=triplet, q=quartet, m=multiplet,
br=broad) and coupling constants (J/Hz) are reported when present
and clearly distinguishable.
Mechanical properties and Oxygen Permeability: Modulus and
elongation tests were conducted according to ASTM D-1708a,
employing an Instron (Model 4502) instrument where the hydrogel
film sample is immersed in borate buffered saline; an appropriate
size of the film sample is gauge length 22 mm and width 4.75 mm,
where the sample further has ends forming a dog bone shape to
accommodate gripping of the sample with clamps of the Instron
instrument, and a thickness of 200+50 microns.
Oxygen permeability (also referred to as Dk) was determined by the
following procedure. Other methods and/or instruments may be used
as long as the oxygen permeability values obtained therefrom are
equivalent to the described method. The oxygen permeability of
silicone hydrogels is measured by the polarographic method (ANSI
Z80.20-1998) using an O2 Permeometer Model 201T instrument
(Createch, Albany, Calif. USA) having a probe containing a central,
circular gold cathode at its end and a silver anode insulated from
the cathode. Measurements are taken only on pre-inspected
pinhole-free, flat silicone hydrogel film samples of three
different center thicknesses ranging from 150 to 600 microns.
Center thickness measurements of the film samples may be measured
using a Rehder ET-1 electronic thickness gauge. Generally, the film
samples have the shape of a circular disk. Measurements are taken
with the film sample and probe immersed in a bath containing
circulating phosphate buffered saline (PBS) equilibrated at
35.degree. C.+/-0.2.degree.. Prior to immersing the probe and film
sample in the PBS bath, the film sample is placed and centered on
the cathode premoistened with the equilibrated PBS, ensuring no air
bubbles or excess PBS exists between the cathode and the film
sample, and the film sample is then secured to the probe with a
mounting cap, with the cathode portion of the probe contacting only
the film sample. For silicone hydrogel films, it is frequently
useful to employ a Teflon polymer membrane, e.g., having a circular
disk shape, between the probe cathode and the film sample. In such
cases, the Teflon membrane is first placed on the pre-moistened
cathode, and then the film sample is placed on the Teflon membrane,
ensuring no air bubbles or excess PBS exists beneath the Teflon
membrane or film sample. Once measurements are collected, only data
with correlation coefficient value (R2) of 0.97 or higher should be
entered into the calculation of Dk value. At least two Dk
measurements per thickness, and meeting R2 value, are obtained.
Using known regression analyses, oxygen permeability (Dk) is
calculated from the film samples having at least three different
thicknesses. Any film samples hydrated with solutions other than
PBS are first soaked in purified water and allowed to equilibrate
for at least 24 hours, and then soaked in PHB and allowed to
equilibrate for at least 12 hours. The instruments are regularly
cleaned and regularly calibrated using RGP standards. Upper and
lower limits are established by calculating a +/-8.8% of the
Repository values established by William J. Benjamin, et al., The
Oxygen Permeability of Reference Materials, Optom Vis Sci 7 (12s):
95 (1997), the disclosure of which is incorporated herein in its
entirety:
TABLE-US-00001 MATERIAL REPOSITORY LOWER UPPER NAME VALUES LIMIT
LIMIT Fluoroperm 30 26.2 24 29 Menicon EX 62.4 56 66 Quantum II
92.9 85 101
TABLE-US-00002 ABBREVIATIONS: NVP 1-Vinyl-2-pyrrolidone TRIS
3-Methacryloxypropyltris(trimethylsiloxy)silane HEMA 2-Hydroxyethyl
methacrylate v-64 2,2'-Azobis(2-methylpropionitrile) EGDMA ethylene
glycol dimethacrylate
##STR00011## Unless otherwise specifically stated or made clear by
its usage, all numbers used in the examples should be considered to
be modified by the term "about" and to be weight percent.
##STR00012##
Example 1
Synthesis of M1-EDS7-TMS
##STR00013##
2,2,5,5-tetramethyl-2,5-disila-1-oxacyclopentane (19.2 g, 0.12 mol)
was taken in 50 mL of dry cyclohexane under N.sub.2 and stirred for
30 min at 25.degree. C. To this mixture lithium trimethylsilanolate
(1.92 g, 0.02 mol) was added with stirring. After 1 h dry THF (25
mL) was added and the reaction mixture continued to stir for 24 h
at 25.degree. C. Dimethylchlorosilane (1.9 g, 0.02 mol) was then
added and the color change was observed. Stirring was continued for
3 h more and the reaction mixture was then filtered. Filtrate was
concentrated under vacuum to give clear oil in 22 g yield as the
expected product based on the method of preparation and
characterized by NMR, SEC and MALDI showing about 7 condensed
2,2,5,5-tetramethyl-2,5-disila-1-oxacyclopentane ring open units.
It was used as such for hydrosilation by taking into toluene (20
mL) and adding allylmethacrylate (3.15 g, 0.025 mol, .about.25
mmol) under N.sub.2 atmosphere followed by the addition of
platinum(0) 1,3-divinyl-1,1,3,3-tetramethyl disiloxane complex 3 wt
% solution in xylene (as catalyst). The reaction mixture was
stirred for 6 h at 40-45.degree. C. Stripping of the solvent on
roto-vap and then high vacuum to gave an yellow oil in 17 g yield
as the desired product characterized by MALDI.
Example 2
Synthesis of M1-EDS6-TMS
To an oven dried 2 L two-neck round bottom flask equipped with a
magnetic stirring bar and condenser under N2 atmosphere were added
2,2,5,5-tetramethyl-2,5-disila-1-oxacyclopentane (77.22 g, 0.482
mol) and anhydrous cyclohexane (150 mL) under stirring in N2
atmosphere. Lithium trimethyl silanolate (7.2 g, 0.0749 mol) was
added to the above reaction mixture followed by the addition of
cyclohexane (25 mL). After stirring for one hour, THF (70 mL,
distilled over Na/Benzophenone) was added and the reaction mixture
continued to stir for 16 hours. Methylacryloxypropyl
dimethylchlorosilane (20 g, 0.09 mol) was then added and the
mixture stirred for another 24 hours. Reaction mixture was then
filtered and Silica gel (3.5 g, dried at 160.degree. C. for 3
hours) was then added and the reaction mixture stirred another 4
hour. Reaction mixture was then filtered thru a bed of Celite (20
g) and BHT (5 mg) was added to the filtrate. The filtrate was then
concentrated under vacuum (40.degree. C./0.3 mm Hg). Heptane (200
mL) was then added to the concentrate with shaking and washed with
DI water (100 mL), aqueous NaHCO3 (2.times.100 mL, prepared by
dissolving 10 g NaHCO3 in 200 mL DI water), brine (100 mL) and
finally DI water (100 mL). Heptane (50 mL) was then added and dried
over MgSO4 (15 g) for 20 hours. MgSO4 was filtered off and the
solvent was removed on rotary evaporator. The crude product was
stirred over activated basic Alumina (30 g for 24 h) and then
filtered over a thin bed of celite Stripping off any residue
solvent at 25.degree. C. at 0.2 mmHg for 30 minutes yielded the
desired product as a clear oil in 80 g quantity. It was
characterized by NMR, GPC, GC-MS and MALDI.
Example 3
Synthesis of M1-EDS9-TMS
2,2,5,5-tetramethyl-2,5-disila-1-oxacyclopentane (14.4 g, 0.09 mol)
was taken in 35 mL of dry cyclohexane under N.sub.2 and stirred for
10 min at 25.degree. C. To this lithium trimethylsilanolate (960
mg, 0.01 mol) was added with stirring. After 2 h dry THF (20 mL)
was added and the reaction mixture continued to stir for 24 h at
25.degree. C. Chlorodimethylsilylpropyloxy methacrylate (2.20 g,
0.01 mol) was then added and the color change was observed.
Stirring was continued for 24 h more and the reaction mixture was
then quenched with 10 mg NaHCO.sub.3. Cyclohexane (10 mL) was added
with continued stirring for 2 h more. Reaction mixture was then
filtered over Celite. Filtrate was concentrated under vacuum to
give clear oil in 16 g yield as the expected product based on the
method of preparation and characterized by NMR, SEC and MALDI
showing about 9 condensed
2,2,5,5-tetramethyl-2,5-disila-1-oxacyclopentane ring open
units.
Example 4
Synthesis of M1-EDS12-TMS
2,2,5,5-tetramethyl-2,5-disila-1-oxacyclopentane (19.2 g, 0.12 mol)
was taken in 50 mL of dry cyclohexane under N.sub.2 and stirred for
30 min at 25.degree. C. To this lithium trimethylsilanolate (960
mg, 0.01 mol) was added with stirring. After 2 h dry THF (20 mL)
was added and the reaction mixture continued to stir for 24 h at
25.degree. C. Chlorodimethylsilylpropyloxy methacrylate (2.20 g,
0.01 mol) was then added and the color change was observed.
Stirring was continued for 24 h more and the reaction mixture was
then filtered over Celite. Filtrate was concentrated under vacuum
to give clear oil in 20 g yield as the expected product based on
the method of preparation and characterized by NMR, SEC and MALDI
showing about 12 condensed
2,2,5,5-tetramethyl-2,5-disila-1-oxacyclopentane ring open
units.
Example 5
Synthesis of M1-EDS15-TMS
2,2,5,5-tetramethyl-2,5-disila-1-oxacyclopentane (24 g, 0.15 mol)
was taken in 60 mL of dry cyclohexane under N.sub.2 and stirred for
10 min at 25.degree. C. To this lithium trimethylsilanolate (960
mg, 0.01 mol) was added with stirring. After 2 h dry THF (20 mL)
was added and the reaction mixture continued to stir for 24 h at
25.degree. C. Chlorodimethylsilylpropyloxy methacrylate (2.20 g,
0.01 mol) was then added and the color change was observed.
Stirring was continued for 24 h more and the reaction mixture was
then quenched with 10 mg NaHCO.sub.3. Cyclohexane (10 mL) was added
with continued stirring for 2 h more. Reaction mixture was then
filtered over Celite. Filtrate was concentrated under vacuum to
give clear oil in 25 g yield as the expected product based on the
method of preparation and characterized by NMR, SEC and MALDI
showing about 15 condensed
2,2,5,5-tetramethyl-2,5-disila-1-oxacyclopentane ring open
units.
Example 6
Synthesis of M1-BIS-EDS3-TMS
##STR00014##
Lithium trimethyl silanolate (19.7 g, 0.2 mol) was suspended in
anhydrous hexane (100 mL) in a 500 mL, round bottom flask was
fitted with a mechanical stirrer, argon gas and a dropping funnel.
A solution of 2,2,5,5-tetramethyl-2,5-disila-1-oxacyclopentane
(32.07 g, 0.2 mol) in anhydrous hexane (100 mL), was quickly added
to the flask with stirring. After an hour, the flask was cooled
with an ice bath and DMF (50 mL) was added with continued stirring.
After 4 h, 3-methacryloxypropyl methyldichlorosilane (29 g, 0.12
mol) was added dropwise to the reaction mixture. The reaction
mixture was stirred further 24 h at room temperature. Deionized
water (50 mL) was then added to the flask with stirred. The organic
layer was separated and dried over anhydrous sodium sulfate and
filtered. The solvent was evaporated on a roto-vap to give the
desired product in 40 g quantity as a clear, yellowish oil. The
product was characterized by GC, GC/MS, IR and NMR.
Example 7
Synthesis of Dimethylammonium Methacrylamide (MA1-Q-EDS9-TMS)
##STR00015## wherein n is as defined above.
2,2,5,5-tetramethyl-2,5-disila-1-oxacyclopentane (48 g, 0.3 mol)
was taken in 55 mL of dry cyclohexane under N.sub.2 and stirred for
30 min at 25.degree. C. To this lithium trimethylsilanolate (4.8 g,
0.05 mol) was added with stirring. After 1 h dry THF (25 mL) was
added and the reaction mixture continued to stir for 24 h at
25.degree. C. Dimethylchlorosilane (5.1 g, 0.55 mol) was then added
and the color change was observed. Stirring was continued for 3 h
more and the reaction mixture was then filtered. Filtrate was
concentrated under vacuum to give clear oil in 42 g yield as the
expected product based on the method of preparation and
characterized by NMR, SEC and MALDI. 28.0 g of this was used for
hydrosilation by taking into toluene (30 mL) and adding
1-bromobutene (4 g, 0.03 mol,) under N.sub.2 atmosphere followed by
the addition of platinum(0) 1,3-divinyl-1,1,3,3-tetramethyl
disiloxane complex 3 wt % solution in xylene (100 uL as catalyst).
The reaction mixture was stirred for 4 h at 45-50.degree. C. and
then at 25.degree. C. for 48 h. The reaction mixture was filtered
over Celite using cotton plug. Stripping of the solvent on roto-vap
and then high vacuum to gave an yellow oil in 27 g yield as the
desired bromo compound characterized by MALDI with n=.about.9
units.
6.6 g (0.004 mol) of the bromo compound and 680 mg (0.004 mol) of
dimethylaminopropyl methacrylamide were mixed together and stirred
under N2 for 6 h at 25.degree. C. Some exotherm was observed.
Reaction mixture was subjected to high vacuum after 10 h to give
the desired product in almost quantitative yield and characterized
by NMR and MALDI.
Example 8
Synthesis of Comparative Monofunctional M1-MCR-C12
##STR00016## wherein n.sup.3 is as defined above
Hydroxy ethoxypropyl terminated polydimethylsiloxane (50 grams,
0.048 mol) available from Gelest, Inc. (MCR-C12) was added to a 500
mL round bottom flask and dried via azeotropic distillation of
toluene. To the flask was added anhydrous methylene chloride (200
mL) and triethylamine (17.12 g, 0.17 mol) and the reaction was
stirred for 20 minutes. The reaction flask was fitted with an
addition funnel which was charged with methacryloyl chloride (17.18
g, 0.16 mol) and an additional 85 mL of anhydrous methylene
chloride. The contents of the addition funnel were added to the
reaction mixture dropwise at which time the addition funnel was
exchanged with a reflux condenser. The reaction was then brought to
reflux for 4 hours. After cooling the reaction mixture was filtered
and placed in a reparatory funnel where it was washed with 2 times
0.1 N HCl (150 mL); 2 times sodium bicarbonate solution (150 mL)
and 2 times Brine solution (150 mL). The organic layer was then
stirred with 10 grams of decolorizing carbon and 10 grams of silica
gel for 24 hours and was then filtered and brought to dryness on a
roto-vap. The reaction yielded 45 g of a clear, yellow oil that was
characterized by GC, NMR, and MALDI.
Example 9
Synthesis of Comparative Monofunctional MCA1-MCR-C12
##STR00017## wherein n.sup.3 is as defined above.
Hydroxy ethoxypropyl terminated polydimethylsiloxane (200 grams,
0.193 mol) available from Gelest, Inc. (MCR-C12) was added to a 2 L
round bottom flask and dried via azeotropic distillation of
toluene. To the flask was added anhydrous methylene chloride (500
mL) and dibutyltin dilaurate (0.474 g, 0.0007 mol). The reaction
flask was fitted with an addition funnel which was charged with
2-Isocyanatoethyl methacrylate (45.0 g, 0.290 mol) and an
additional 100 mL of anhydrous methylene chloride. The contents of
the addition funnel were added to the reaction mixture dropwise and
the reaction then stirred for 48 hours. 50 grams of silica gel (EMD
Silica gel 60) are then added to the reaction and stirred for 24
hours to scavenge excess isocyanatoethyl methacrylate. The reaction
is then filtered and concentrated on a roto-vap yielding 210 g of a
clear oil that was characterized by GC, NMR, and MALDI.
TABLE-US-00003 TABLE 1 Examples 10-23. Formulation of various EDS
based monomers and comparative examples Ma2D37 TRIS [tris
2-Hydroxy- Methacryl- (trimethylsiloxy) N-Vinyl N,N- ethyl M1-
MCa1- amide silylpropyl Pyroli- Dimethyl- metha- MCR- MCR- M1-EDS7-
M1-EDS6- M1-EDS9- Example Crosslinker methacrylate] done acrylamide
crylate Hexanol C12 C12 - TMS TMS TMS 10 9.5 35.5 30.8 4.7 4.7 4.7
9.5 x x x x 11 9.5 35.5 30.8 4.7 4.7 4.7 x 9.5 x x x 12 9.5 35.5
30.8 4.7 4.7 4.7 x x 9.5 x x 13 9.5 35.5 30.8 4.7 4.7 4.7 x x x 9.5
x 14 9.5 35.5 30.8 4.7 4.7 4.7 x x x x 9.5 15 9.5 35.5 30.8 4.7 4.7
4.7 x x x x x 16 9.5 35.5 30.8 4.7 4.7 4.7 x x x x x 17 0.0 29.9
25.9 4.0 4.0 19.9 x x x x 8.0 18 0.0 32.5 28.1 4.3 4.3 13.0 x x x x
8.7 19 9.5 35.5 30.8 4.7 4.7 4.7 x x x x x 20 9.5 35.5 30.8 4.7 4.7
4.7 x x x x x 21 9.5 35.5 30.8 4.7 4.7 4.7 x x x x x 22 9.5 35.5
30.8 4.7 4.7 4.7 x x x x x 23 9.5 35.5 30.8 4.7 4.7 4.7 x x x x x
M1-Bis- Ma1-Q- V1- IMVT M1-EDS12- M1-EDS15- M2- M2-D27- M1-Bis-
EDS3- EDS9- MCR- VCa1- Darocur (c- oncentration Example TMS TMS
EDS23 EDS10 D3-TMS TMS TMS C12 MCR-C12 1173 in ppm) 10 x x x x x x
x x x 0.47 90 11 x x x x x x x x x 0.47 90 12 x x x x x x x x x
0.47 90 13 x x x x x x x x x 0.47 90 14 x x x x x x x x x 0.47 90
15 9.5 x x x x x x x x 0.47 90 16 x 9.5 x x x x x x x 0.47 90 17 x
x 8.0 x x x x x x 0.47 90 18 x x x 8.7 x x x x x 0.47 90 19 x x x x
9.5 x x x x 0.47 90 20 x x x x x 9.5 x x x 0.47 90 21 x x x x x x
9.5 x x 0.47 90 22 x x x x x x x 9.5 x 0.47 90 23 x x x x x x x x
9.5 0.47 90 Note: The amounts presented in the table above are
weight percentages in the formulation. Tint level is in ppm.
Preparation Procedure:
For examples 10-15, 17-23, 32, 54-56 and 69, the specific monomer
mixes set forth were prepared according to the table 1 above and
tables 3 and 5 below by weighing out various weight percentages of
the components. Monomer mix was dispensed between polypropylene
molds and prepared as lenses or flats in the case of Dk samples.
Polymerization was carried out under UV light (.about.350 nm) for a
period of two hours. After polymerization, the lenses or flats were
released from the molds using 33% IPA in water and then extracted
in 100% IPA for 4 hours. Lenses/Flats were then placed in deionized
water for 30 minutes and packaged in vials containing 4 mL of
borate buffered saline (BBS). Measured properties for the
lenses/flats are shown in the table below.
TABLE-US-00004 TABLE 2 Selected Properties of processed
lenses/flats containing EDS monomers and comparative examples.
Water Dk Modulus Elongation Tear Strength Advancing Contact
Receding Contact Example Content (%) (barrers) (gm/sqmm) (%)
(gm/mm) Angle Angle Hysteressis 10 42.3 96 92 (10) 125 (52) 7 (1)
28 (4) 19 (0) 9 (4) 11 43.0 x 107 (10) 100 (30) 4 (1) 29 (2) 21 (1)
8 (1) 12 47.3 93 58 (6) 100 (30) 4 (1) 29 (2) 21 (1) 8 (1) 13 40.8
87 91 (9) 177 (25) 5 (1) 29 (3) 21 (3) 8 (6) 14 42.1 x .3/17 .3/17
.3/17 x x x 15 35.7 x .3/17 .3/17 .3/17 x x x 16 ND ND ND ND ND ND
ND ND 17 42.0 95 74 (4) 236 (25) 7 (1) x x x 18 41.6 85 66 (5) 143
(43) 6 (1) 19 40.9 x 137 (6) 157 (22) x x x x 20 32.0 x 137 (8) 137
(20) x x x x 21 43.1 x 140 (6) 96 (14) x x x x 22 41.9 x 98 (10)
159 (29) 6 (0.4) 98 (2) 21 (1) 76 (1) 23 39.2 x 105 (5) 125 (23) 5
(1) 96 (5) 21 (1) 76 (5) 32 46.9 91 71 (8) 165 (74) x 31 (6) 16 (1)
15 (5) 54 44.9 x 84 (10) 177 (31) 4 (1) 33 (0.7) 19 (1.0) 14 (1.6)
55 43.2 x 80 (7) 176 (60) 7 (1) 40 (7.0) 24 (2.3) 16 (9.2) 56 43.3
x 72 (4) 159 (68) 7 (0.3) 41 (2.0) 22 (1.4) 19 (0.6) 69 32.0 x 137
(8) 137 (20) x x x x
A 4502 Mechanical Tester MTS Instron was used to measure the
modulus, tensile strength, percent elongation and tear strength of
the lenses. Samples were tested in a water bath containing borate
buffered saline.
Captive bubble contact angle data was collected on a First Ten
Angstroms FTA-1000 prop Shape Instrument. All samples were rinsed
in HPLC grade water prior to analysis in order to remove components
of the packaging solution from the sample surface. Prior to data
collection the surface tension of the water used for all
experiments was measured using the pendant drop method. In order
for the water to qualify as appropriate for use, a surface tension
value of 70-72 dynes/cm was expected. All lens samples were placed
onto a curved sample holder and submerged into a quartz cell filled
with HPLC grade water. Receding and advancing captive bubble
contact angles were collected for each sample. The receding contact
angle is defined as the angle measured in water as the air bubble
is expanding across the sample surface (water is receding from the
surface). The advancing contact angle is defined as the angle
measured in water as the air bubble is retracting from the lens
surface (water is advancing across the surface). All captive bubble
data was collected using a high speed digital camera focused onto
the sample/air bubble interface. The contact angle was calculated
at the digital frame just prior to contact line movement across the
sample/air bubble interface.
TABLE-US-00005 TABLE 3 Further examples of monomer mix
formulations. Ma2D37 TRIS [tris IMVT Methacrylamide
(trimethylsiloxy) N-Vinyl N,N-Dimethyl- 2-Hydroxyethyl M1-EDS6-
Darocur (concentration Example Crosslinker silylpropyl
methacrylate] Pyrolidone acrylamide methacrylate Hexanol TMS 1173
in ppm) 24 0.1 41.2 58.1 0.0 0.0 0.0 0.1 0.48 90 25 4.7 38.4 29.2
1.9 7.6 4.4 13.3 0.47 90 26 7.0 30.5 20.5 3.0 7.0 4.7 27.0 0.48 90
27 11.1 29.4 27.7 2.6 6.0 4.0 18.8 0.43 90 28 32.3 28.0 13.8 4.3
4.3 4.0 12.9 0.43 90 29 44.7 12.9 23.0 0.0 4.2 3.9 10.9 0.42 90 30
59.7 9.6 14.3 0.0 4.8 4.5 6.7 0.48 90 31 75.8 0.0 0.0 9.5 9.5 4.7
0.1 0.47 90 32 6.6 35.5 30.8 4.7 4.7 4.7 12.3 0.47 90 33 4.5 9.0
58.8 4.5 0.0 13.6 9.1 0.45 90 34 6.1 18.2 18.2 1.2 1.2 48.6 6.1
0.30 90 35 7.7 23.1 23.1 1.5 1.5 34.6 7.7 0.48 90 36 15.9 15.9 23.9
4.0 4.0 19.9 15.9 0.40 90 37 5.0 10.0 29.9 5.0 5.0 14.9 29.9 0.50
90 Note: The amounts presented in the table above are weight
percentages in the formulation. Tint level is in ppm.
TABLE-US-00006 TABLE 4 Further examples of monomer mix
formulations. Ma2D37 TRIS [tris IMVT Methacrylamide
(trimethylsiloxy) N-Vinyl N,N-Dimethyl- 2-Hydroxyethyl M1-EDS6-
Darocur (concentration Example Crosslinker silylpropyl
methacrylate] Pyrolidone acrylamide methacrylate Hexanol TMS 1173
in ppm) 38 0.1 41.2 58.1 0.0 0.0 0.0 0.1 0.48 145 39 4.7 38.4 29.2
1.9 7.6 4.4 13.3 0.47 145 40 7.0 30.5 20.5 3.0 7.0 4.7 27.0 0.48
145 41 11.1 29.4 27.7 2.6 6.0 4.0 18.8 0.43 145 42 32.3 28.0 13.8
4.3 4.3 4.0 12.9 0.43 145 43 44.7 12.9 23.0 0.0 4.2 3.9 10.9 0.42
145 44 59.7 9.6 14.3 0.0 4.8 4.5 6.7 0.48 145 45 75.8 0.0 0.0 9.5
9.5 4.7 0.1 0.47 145 46 6.6 35.5 30.8 4.7 4.7 4.7 12.3 0.47 145 47
4.5 9.0 58.8 4.5 0.0 13.6 9.1 0.45 145 48 6.1 18.2 18.2 1.2 1.2
48.6 6.1 0.30 145 49 7.7 23.1 23.1 1.5 1.5 34.6 7.7 0.48 145 50
15.9 15.9 23.9 4.0 4.0 19.9 15.9 0.40 145 51 5.0 10.0 29.9 5.0 5.0
14.9 29.9 0.50 145 Note: The amounts presented in the table above
are weight percentages in the formulation. Tint level is in
ppm.
TABLE-US-00007 TABLE 5 Further examples of monomer mix
formulations. TRIS [tris Ma2D37 (trimethyl- 2-Hydroxy- IMVT
Methacryl- siloxy) N,N- ethyl M1- M1-BIS- (concen- amide
silylpropyl N-Vinyl Dimethyl- meth- t-Amyl EDS6- EDS3- Darocur
tration Example Crosslinker methacrylate] Pyrolidone acrylamide
acrylate Hexanol N- onanol alcohol TMS TMS 1173 in ppm) 52 0.1 41.2
58.1 0.0 0.0 0.0 5.1 0.0 0.1 0.0 0.1 200 53 4.7 38.4 29.2 1.9 7.6
4.4 4.4 0.0 13.3 0.0 0.47 200 54 6.6 35.6 30.8 4.7 4.7 4.7 0.0 0.0
12.3 0.0 0.47 200 55 6.6 35.6 30.8 4.7 4.7 0.0 4.7 0.0 12.3 0.0
0.47 200 56 6.6 35.6 30.8 4.7 4.7 0.0 0.0 4.7 12.3 0.0 0.47 200 57
7.0 30.5 20.5 3.0 7.0 0.0 4.7 0.0 27.0 0.0 0.48 200 58 11.1 29.4
27.7 2.6 6.0 4.0 0.0 0.0 18.8 0.0 0.43 200 59 32.3 28.0 13.8 4.3
4.3 0.0 0.0 4.0 12.9 0.0 0.43 200 60 44.7 12.9 23.0 0.0 4.4 0.0 3.9
0.0 10.9 0.0 0.2 200 61 59.7 9.6 14.3 0.0 4.8 0.0 0.0 4.5 6.7 0.0
0.48 200 62 75.8 0.0 0.0 9.5 9.5 4.7 0.0 0.0 0.1 0.0 0.47 200 63
6.6 35.5 30.8 4.7 4.7 4.7 0.0 0.0 12.3 0.0 0.47 200 64 4.5 9.0 58.8
4.5 0.0 0.0 13.6 0.0 9.1 0.0 0.45 200 65 6.1 18.2 18.2 1.2 1.2 0.0
0.0 48.6 6.1 0.0 0.30 200 66 7.7 23.1 23.1 1.5 1.5 34.6 0.0 0.0 7.7
0.0 0.48 200 67 15.9 15.9 23.9 4.0 4.0 0.0 19.9 0.0 15.9 0.0 0.40
200 68 5.0 10.0 29.9 5.0 5.0 0.0 0.0 14.9 29.9 0.0 0.50 200 69 9.5
35.5 30.8 4.7 4.7 4.7 4.7 0.0 0.0 9.5 0.47 60 Note: The amounts
presented in the table above are weight percentages in the
formulation. Tint level is in ppm.
Disclosed in certain preferred embodiments of the invention herein
is:
1. A monomer having a structural formula (I):
##STR00018## wherein X is the residue of a ring opening agent, L is
the same or different and is a linker group or a bond and V is an
ethylenically unsaturated polymerizable group, R.sub.1, R.sub.2,
R.sub.3, R.sub.4, R.sub.5, R.sub.6 are independently H, alkyl, halo
alkyl, cyclo alkyl, heterocyclo alkyl, alkenyl, halo alkenyl, or
aromatic, R.sub.7 and R.sub.8 are independently H or alkyl wherein
at least one of R.sub.7 or R.sub.8 is hydrogen, y is 2-7 and n is
1-100. 2. A monomer having a structural formula (II)
##STR00019## wherein L is the same or different and is a linker
group or a bond and V is the same or different and is an
ethylenically unsaturated polymerizable group, R.sub.1, R.sub.2,
R.sub.3, R.sub.4, R.sub.5, R.sub.6 and R.sub.9 are independently H,
alkyl, halo alkyl, cyclo alkyl, heterocyclo alkyl, alkenyl, halo
alkenyl, or aromatic, R.sub.7 and R.sub.8 are independently H or
alkyl wherein at least one of R.sub.7 or R.sub.8 is hydrogen, y is
2-7 and n is 1-100. 3. A monomer according to claim 1 wherein the X
is a residue of a ring opening agent selected from the group
consisting of alkyl lithiums, alkoxides, trialkylsiloxylithiums and
acrylic ester-capped polysiloxane prepolymers in the presence of an
acid catalyst. 4. The monomer of claim 3 wherein the residue of the
ring opening agent contains halo atoms. 5. The monomer of claim 1
wherein linker group is selected from the group consisting of
substituted or unsubstituted alkyl, alkyl ether, alkenyls, alkenyl
ethers, halo alkyls, substituted or unsubstituted siloxanes, and
monomers capable of propagating ring opening. 6. The monomer of
claim 2 wherein linker group is selected from the group consisting
of substituted or unsubstituted alkyl, alkyl ether, alkenyls,
alkenyl ethers, halo alkyls, substituted or unsubstituted
siloxanes, and monomers capable of propagating ring opening. 7. The
monomer of claim 1 having a structural formula (III):
##STR00020## wherein R.sub.9, R.sub.10 and R.sub.11 are
independently H, alkyl, haloalkyl or other substituted alkyl
groups, n is 1-100 and n.sup.1 is 0-10. 8. The monomer of claim 1
having a structural formula (IV):
##STR00021## wherein n is 1-100. 9. The monomer of claim 8 wherein
n is 2-80. 10. The monomer of claim 8 wherein n is 3-20. 11. The
monomer of claim 8 wherein n is 5-15. 12. A monomer of claim 1
wherein V is selected from the group consisting of acrylates,
methacrylates, vinyl carbonates, O-vinyl carbamates, N-vinyl
carbamates, acrylamides and methacrylamides. 13. A monomer of claim
2 wherein V is selected from the group consisting of acrylates,
methacrylates, vinyl carbonates, O-vinyl carbamates, N-vinyl
carbamates, acrylamides and methacrylamides. 14. The monomer of
claim 1 having a structural formula selected from the group
consisting of the following structural formulae:
##STR00022##
##STR00023## 15. The monomer of claim 1 having a structural formula
selected from the group consisting of the following structural
formulae:
##STR00024## wherein R.sub.9, R.sub.10 and R.sub.11 are
independently H, alkyl, haloalkyl or other substituted alkyl groups
and n is 1-100 and n.sup.1 is 0-10. 16. The monomer of claim 1
having a structural formula selected from the group consisting of
the following structural formulae:
##STR00025## wherein n is 1-100 and X.sup.- is a counterion to
provide an overall neutral charge. 17. The monomer of claim 1
having the following structural formula:
##STR00026## 18. A monomer mix useful for forming a medical device
wherein the monomer mix comprises at least one monomer selected
from the group consisting of the monomers of claim 1 and when
polymerized forms a medical device. 19. A monomer mix useful for
forming a medical device wherein the monomer mix comprises at least
one monomer selected from the group consisting of the monomers of
claim 2 and when polymerized forms a medical device. 20. The
monomer mix of claim 18 further comprising a second copolymerizable
second monomer. 21. The monomer mix of claim 19 further comprising
a second copolymerizable second monomer. 22. The monomer mix of
claim 18 wherein the medical device formed is selected from the
group consisting of rigid contact lenses, soft contact lenses,
phakic intraocular lenses, aphakic intraocular lenses and corneal
implants. 23. The monomer mix of claim 19 wherein the medical
device formed is selected from the group consisting of rigid
contact lenses, soft contact lenses, phakic intraocular lenses,
aphakic intraocular lenses and corneal implants. 24. The monomer
mix of claim 18 wherein the medical device formed is selected from
the group consisting of artificial heart valves, films, surgical
devices, vessel substitutes, intrauterine devices, membranes,
diaphragms, surgical implants, artificial blood vessels, artificial
ureters, artificial breast tissue, membranes intended to come into
contact with body fluid outside of the body, membranes for kidney
dialysis machines, membranes for heart/lung machines, catheters,
mouth guards, denture liners, ophthalmic devices, and hydrogel
contact lenses. 25. The monomer mix of claim 19 wherein the medical
device formed is selected from the group consisting of artificial
heart valves, films, surgical devices, vessel substitutes,
intrauterine devices, membranes, diaphragms, surgical implants,
artificial blood vessels, artificial ureters, artificial breast
tissue, membranes intended to come into contact with body fluid
outside of the body, membranes for kidney dialysis machines,
membranes for heart/lung machines, catheters, mouth guards, denture
liners, ophthalmic devices, and hydrogel contact lenses. 26. The
monomer mix of claim 24 wherein the medical device is a hydrogel
contact lens. 27. The monomer mix of claim 25 wherein the medical
device is a hydrogel contact lens. 28. The monomer mix of claim 18
wherein the at least one monomer selected from the group consisting
of the monomers of claim 1 is an mono ethylenically unsaturated
polycarbosiloxane monomer. 29. The monomer mix of claim 19 wherein
the at least one monomer selected from the group consisting of the
monomers of claim 2 is an mono ethylenically unsaturated
polycarbosiloxane monomer. 30. The monomer mix of claim 28 wherein
the mono ethylenically unsaturated polycarbosiloxane monomer is
present in an amount from about 0.1 to about 30 percent by weight
of the monomer mix. 31. The monomer mix of claim 28 wherein the
mono ethylenically unsaturated polycarbosiloxane monomer is present
in an amount from about 0.1 to about 20 percent by weight of the
monomer mix. 32. The monomer mix of claim 28 wherein the mono
ethylenically unsaturated polycarbosiloxane monomer is present in
an amount from about 5 to about 15 percent by weight of the monomer
mix. 33. The monomer mix of claim 29 wherein the mono ethylenically
unsaturated polycarbosiloxane monomer is present in an amount from
about 0.1 to about 30 percent by weight of the monomer mix. 34. The
monomer mix of claim 29 wherein the mono ethylenically unsaturated
polycarbosiloxane monomer is present in an amount from about 0.1 to
about 20 percent by weight of the monomer mix. 35. The monomer mix
of claim 29 wherein the mono ethylenically unsaturated
polycarbosiloxane monomer is present in an amount from about 5 to
about 15 percent by weight of the monomer mix. 36. The monomer mix
of claim 20 wherein the second copolymerizable second monomer is a
hydrophobic silicone containing monomer. 37. The monomer mix of
claim 36 wherein the hydrophobic silicone containing monomer is
present in the monomer mix between about 0.1 to about 75.8 percent
by weight. 38. The monomer mix of claim 36 wherein the hydrophobic
silicone containing monomer is present in the monomer mix between
about 2 to about 20 percent by weight. 39. The monomer mix of claim
36 wherein the hydrophobic silicone containing monomer is present
in the monomer mix between about 5 to about 13 percent by weight.
40. The monomer mix of claim 21 wherein the second copolymerizable
second monomer is a hydrophobic silicone containing monomer. 41.
The monomer mix of claim 40 wherein the hydrophobic silicone
containing monomer is present in the monomer mix between about 0.1
to about 75.8 percent by weight. 42. The monomer mix of claim 40
wherein the hydrophobic silicone containing monomer is present in
the monomer mix between about 2 to about 20 percent by weight. 43.
The monomer mix of claim 40 wherein the hydrophobic silicone
containing monomer is present in the monomer mix between about 5 to
about 13 percent by weight. 44. The monomer mix of claim 20 wherein
the second copolymerizable monomer is a non-silicone containing
hydrophobic monomer. 45. The monomer mix of claim 21 wherein the
second copolymerizable monomer is a non-silicone containing
hydrophobic monomer. 46. The monomer mix of claim 20 wherein the
non-silicone containing hydrophobic monomer is present at about 0
to about 60 percent by weight. 47. The monomer mix of claim 21
wherein the non-silicone containing hydrophobic monomer is present
at about 0 to about 60 percent by weight. 48. The monomer mix of
claim 20 wherein the non-silicone containing hydrophobic monomer is
selected from the group consisting of alkyl acrylates and alkyl
methacrylates. 49. The monomer mix of claim 21 wherein the
non-silicone containing hydrophobic monomer is selected from the
group consisting of alkyl acrylates and alkyl methacrylates. 50.
The monomer mix of claim 20 wherein the second copolymerizable
monomer is a bulky monomers selected from the group consisting of
methacryloxypropyl tris(trimethylsiloxy)silane ("TRIS"),
pentamethyldisiloxanyl methylmethacrylate,
tris(trimethylsiloxy)methacryloxy propylsilane,
phenyltretramethyl-disloxanylethyl acrylate,
methyldi(trimethylsiloxy)methacryloxymethyl silane,
3-[tris(trimethylsiloxy)silyl]propyl vinyl carbamate,
3[tris(trimethylsiloxy)silyl]propyol allyl carbamate, and
3-[tris(trimethylsiloxy)silyl]propyl vinyl carbonate. 51. The
monomer mix of claim 21 wherein the second copolymerizable monomer
is a bulky monomers selected from the group consisting of
methacryloxypropyl tris(trimethylsiloxy)silane ("TRIS"),
pentamethyldisiloxanyl methylmethacrylate,
tris(trimethylsiloxy)methacryloxy propylsilane,
phenyltretramethyl-disloxanylethyl acrylate,
methyldi(trimethylsiloxy)methacryloxymethyl silane,
3-[tris(trimethylsiloxy)silyl]propyl vinyl carbamate,
3[tris(trimethylsiloxy)silyl]propyol allyl carbamate, and
3-[tris(trimethylsiloxy)silyl]propyl vinyl carbonate. 52. The
monomer mix of claim 50 wherein the bulky monomer is present at
about 0 to about 41.2 percent by weight. 53. The monomer mix of
claim 50 wherein the bulky monomer is present at about 34 to about
41 percent by weight. 54. The monomer mix of claim 50 wherein the
bulky monomer is present at about 0 to about 25 to about 41 percent
by weight. 55. The monomer mix of claim 51 wherein the bulky
monomer is present at about 0 to about 41.2 percent by weight. 56.
The monomer mix of claim 51 wherein the bulky monomer is present at
about 34 to about 41 percent by weight. 57. The monomer mix of
claim 51 wherein the bulky monomer is present at about 0 to about
25 to about 41 percent by weight. 58. The monomer mix of claim 26
wherein the monomer mix comprises a mixture containing at least one
silicone-containing monomer and at least one hydrophilic monomer.
59. The monomer mix of claim 26 wherein the monomer mix comprises a
separate crosslinker. 60. The monomer mix of claim 59 wherein the
separate crosslinker is selected from the group consisting of
methacrylates, ethylene glycol dimethacrylate (EGDMA) and allyl
methacrylate (AMA). 61. The monomer mix of claim 60 wherein the
separate crosslinker is present at between about 0 to about 76
percent by weight. 62. The monomer mix of claim 60 wherein the
separate crosslinker is present at between about 2 to about 20
percent by weight. 63. The monomer mix of claim 60 wherein the
separate crosslinker is present at between about 5 to about 13
percent by weight. 64. The monomer mix of claim 27 wherein the
silicone-containing monomer is a crosslinking agent. 65. The
monomer mix of claim 20 wherein the second copolymerizable monomer
is a hydrophilic monomer. 66. The monomer mix of claim 65 wherein
the hydrophilic monomer is selected from the group consisting of
unsaturated carboxylic acids, methacrylic acids, acrylic acids;
acrylic substituted alcohols, 2-hydroxyethyl methacrylate,
2-hydroxyethyl acrylate; vinyl lactams, N-vinylpyrrolidone (NVP),
1-vinylazonan-2-one; acrylamides, methacrylamide,
N,N-dimethylacrylamide (DMA) and mixtures thereof. 67. The monomer
mix of claim 65 wherein the hydrophilic monomer is present,
separately or by combined weight in amounts of between about 0 to
about 60 percent by weight. 68. The monomer mix of claim 65 wherein
the hydrophilic monomer is present, separately or by combined
weight in amounts between about 20 to about 45 percent by weight.
69. The monomer mix of claim 65 wherein the hydrophilic monomer is
present, separately or by combined weight in amounts between about
0 to about 48.6 percent by weight. 70. The monomer mix of claim 65
wherein the hydrophilic monomer is present, separately or by
combined weight in amounts between about 0 to about 30 percent by
weight. 71. The monomer mix of claim 65 wherein the hydrophilic
monomer is present, separately or by combined weight in amounts
between about 0 to about 25 percent by weight. 72. The monomer mix
of claim 65 wherein the hydrophilic monomer is present, separately
or by combined weight in amounts between about 0 to about 9.5
percent by weight. 73. The monomer mix of claim 65 wherein the
hydrophilic monomer is present, separately or by combined weight in
amounts between about 2 to about 7 percent by weight. 74. The
monomer mix of claim 21 wherein the second copolymerizable monomer
is a hydrophilic monomer. 75. The monomer mix of claim 74 wherein
the hydrophilic monomer is selected from the group consisting of
unsaturated carboxylic acids, methacrylic acids, acrylic acids;
acrylic substituted alcohols, 2-hydroxyethyl methacrylate,
2-hydroxyethyl acrylate; vinyl lactams, N-vinylpyrrolidone (NVP),
1-vinylazonan-2-one; acrylamides, methacrylamide,
N,N-dimethylacrylamide (DMA) and mixtures thereof. 76. The monomer
mix of claim 74 wherein the hydrophilic monomer is present,
separately or by combined weight in amounts of between about 0 to
about 60 percent by weight. 77. The monomer mix of claim 74 wherein
the hydrophilic monomer is present, separately or by combined
weight in amounts between about 20 to about 45 percent by weight.
78. The monomer mix of claim 74 wherein the hydrophilic monomer is
present, separately or by combined weight in amounts between about
0 to about 48.6 percent by weight. 79. The monomer mix of claim 74
wherein the hydrophilic monomer is present, separately or by
combined weight in amounts between about 0 to about 30 percent by
weight. 80. The monomer mix of claim 74 wherein the hydrophilic
monomer is present, separately or by combined weight in amounts
between about 0 to about 25 percent by weight. 81. The monomer mix
of claim 74 wherein the hydrophilic monomer is present, separately
or by combined weight in amounts between about 0 to about 9.5
percent by weight. 82. The monomer mix of claim 74 wherein the
hydrophilic monomer is present, separately or by combined weight in
amounts between about 2 to about 7 percent by weight. 83. The
monomer mix of claim 36 further comprising an organic diluent. 84.
The monomer mix of claim 83 wherein the organic diluent is selected
from the group consisting of alcohols, tert-butanol (TBA),
tert-amyl alcohol, hexanol and nonanol; diols, ethylene glycol;
polyols, glycerol and mixtures thereof. 85. The monomer mix of
claim 83 wherein the organic diluent is present at about 0 to about
60% by weight of the monomeric mixture. 86. The monomer mix of
claim 83 wherein the organic diluent is present at about 1 to about
40% by weight. 87. The monomer mix of claim 83 wherein the organic
diluent is present at about 2 to about 30% by weight. 88. The
monomer mix of claim 83 wherein the organic diluent is present at
about 3 to about 25% by weight. 89. The monomer mix of claim 40
further comprising an organic diluent. 90. The monomer mix of claim
89 wherein the organic diluent is selected from the group
consisting of alcohols, tert-butanol (TBA), tert-amyl alcohol,
hexanol and nonanol; diols, ethylene glycol; polyols, glycerol and
mixtures thereof. 91. The monomer mix of claim 89 wherein the
organic diluent is present at about 0 to about 60% by weight of the
monomeric mixture. 92. The monomer mix of claim 89 wherein the
organic diluent is present at about 1 to about 40% by weight. 93.
The monomer mix of claim 89 wherein the organic diluent is present
at about 2 to about 30% by weight. 94. The monomer mix of claim 89
wherein the organic diluent is present at about 3 to about 25% by
weight. 95. A hydrogel contact lens comprising a polymerized
monomer mix comprising a polymerizable monomer mixture comprising
about 0.1 to about 75.8 percent by weight of a methacrylamide
crosslinker, about 0 to about 41.2 percent by weight of a bulky
siloxane monomer, about 0 to about 78 percent by weight of at least
one hydrophilic monomer, about 0 to about 48.6 percent by weight of
an alcohol, about 0.1 to about 29.9 weight percent of an mono
ethylenically unsaturated polycarbosiloxane monomer, about 0.1 to
about 1.0 percent by weight of an initiator and about 90 to about
200 parts per million of a visibility tint. 96. The hydrogel
contact lens of claim 95 comprising as part of polymerizable
monomer mixture comprising about 5 to about 13 percent by weight of
a methacrylamide crosslinker, about 34 to about 41 percent by
weight of a bulky siloxane monomer, about 28 to about 52 percent by
weight of at least one hydrophilic monomer, about 0 to about 25
percent by weight of an alcohol, about 5 to about 15 weight percent
of an mono ethylenically unsaturated polycarbosiloxane monomer,
about 0.2 to about 0.8 percent by weight of an initiator and about
90 to about 145 parts per million of a visibility tint. 97. The
hydrogel contact lens of claim 95 comprising as part of
polymerizable monomer mixture comprising about 2 to about 8 percent
by weight of a methacrylamide crosslinker, about 25 to about 38
percent by weight of a bulky siloxane monomer, about 35 to about 45
percent by weight of at least one hydrophilic monomer, about 3 to
about 8 percent by weight of an alcohol, about 10 to about 13
weight percent of an mono ethylenically unsaturated
polycarbosiloxane monomer, about 0.3 to about 0.6 percent by weight
of an initiator and about 145 to about 200 parts per million of a
visibility tint.
It will be understood that various modifications may be made to the
embodiments disclosed herein. Therefore the above description
should not be construed as limiting, but merely as exemplifications
of preferred embodiments. For example, the functions described
above and implemented as the best mode for operating the present
invention are for illustration purposes only. Other arrangements
and methods may be implemented by those skilled in the art without
departing from the scope and spirit of this invention. Moreover,
those skilled in the art will envision other modifications within
the scope and spirit of the features and advantages appended
hereto.
* * * * *